WO2022054387A1 - Encre d'impression à jet d'encre et procédé d'impression à jet d'encre - Google Patents

Encre d'impression à jet d'encre et procédé d'impression à jet d'encre Download PDF

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Publication number
WO2022054387A1
WO2022054387A1 PCT/JP2021/025956 JP2021025956W WO2022054387A1 WO 2022054387 A1 WO2022054387 A1 WO 2022054387A1 JP 2021025956 W JP2021025956 W JP 2021025956W WO 2022054387 A1 WO2022054387 A1 WO 2022054387A1
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Prior art keywords
ink
ring
group
meth
inkjet recording
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PCT/JP2021/025956
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English (en)
Japanese (ja)
Inventor
博道 沼澤
大輔 佐々木
優介 坂井
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN202180061669.XA priority Critical patent/CN116096576A/zh
Priority to EP21866347.4A priority patent/EP4212341A4/fr
Priority to JP2022547414A priority patent/JP7451730B2/ja
Publication of WO2022054387A1 publication Critical patent/WO2022054387A1/fr
Priority to US18/167,880 priority patent/US20230203330A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J11/00—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
    • B41J11/0015—Devices or arrangements  of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
    • B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
    • B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/007—Squaraine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
    • C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • This disclosure relates to an ink jet recording ink and an inkjet recording method.
  • the near-infrared absorbing dye that absorbs infrared rays without substantially absorbing visible light has invisibility and is expected to be applied in the ink field.
  • Japanese Patent Application Laid-Open No. 2019-001983 describes an inkjet ink containing a squarylium dye, a dispersant, an organic solvent, and water.
  • an inkjet recording ink and an inkjet capable of obtaining an image recording material having excellent readability and readability after a lapse of time is provided.
  • This disclosure includes the following aspects.
  • ⁇ 1> Contains a near-infrared absorbing dye represented by the following formula 1, a polymerizable monomer, a polymerization initiator, and a dispersant, and the content of the polymerizable monomer is 50% by mass or more with respect to the total amount of the ink for inkjet recording.
  • Ink for inkjet recording wherein the difference between the SP value of the polymerizable monomer and the SP value of the dispersant is 3.8 MPa 1/2 to 16.0 MPa 1/2 .
  • rings A and B each independently represent an aromatic or heteroaromatic ring
  • X A and X B each independently represent a monovalent substituent
  • GA and GB independently.
  • n A and n B are the largest of GA and GB that can be substituted with ring A or ring B , respectively.
  • X A and GA may be coupled to each other to form a ring
  • X B and GB may be coupled to each other to form a ring
  • GA and GB may be coupled to each other to form a ring, respectively.
  • the GAs and the GBs may be coupled to each other to form a ring structure.
  • ⁇ 2> The ink jet recording ink according to ⁇ 1>, wherein the dispersant has a weight average molecular weight of 50,000 or less.
  • ⁇ 3> The ink jet recording ink according to ⁇ 1> or ⁇ 2>, wherein the dispersant is a block polymer.
  • ⁇ 4> The ink jet recording ink according to any one of ⁇ 1> to ⁇ 3>, which further contains a pigment derivative.
  • ⁇ 5> The ink jet recording ink according to any one of ⁇ 1> to ⁇ 4>, which further contains a siloxane compound.
  • ⁇ 6> The ink jet recording ink according to ⁇ 5>, wherein the siloxane compound contains a siloxane compound having a polymerizable group.
  • ⁇ 7> The inkjet recording ink according to ⁇ 6>, wherein the content of the siloxane compound having a polymerizable group is 0.5% by mass to 3% by mass with respect to the total amount of the inkjet recording ink.
  • ⁇ 8> The ink jet recording ink according to any one of ⁇ 1> to ⁇ 7>, wherein the polymerization initiator contains an acylphosphine oxide compound and a thioxanthone compound.
  • ⁇ 9> The inkjet recording according to any one of ⁇ 1> to ⁇ 8>, wherein the proportion of the polymerizable monomer having a glass transition temperature of 30 ° C. or higher in the polymerizable monomer is 90% by mass or more. ink.
  • the inkjet recording ink according to any one of ⁇ 1> to ⁇ 9> is used, and a step of ejecting the inkjet recording ink onto the substrate by an inkjet recording method and an ejection onto the substrate.
  • An inkjet recording method including a step of irradiating the ink jet recording ink with active energy rays.
  • an ink jet recording ink and an inkjet recording method capable of obtaining an image recording material having excellent readability and readability after a lapse of time are provided.
  • the numerical range indicated by using "-" in the present specification means a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means. In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.
  • the term "process" is included in this term as long as the intended purpose of the process is achieved, not only in an independent process but also in cases where it cannot be clearly distinguished from other processes. Is done.
  • (meth) acrylate is a concept including both acrylate and methacrylate.
  • (meth) acrylic is a concept that includes both acrylic and methacrylic.
  • the "readability after a lapse of time” means the readability of an image recorded material obtained by using an ink in which a predetermined time (for example, one week) has passed after preparation.
  • the inkjet recording ink of the present disclosure (hereinafter, simply referred to as “ink”) contains a near-infrared absorbing dye represented by the following formula 1, a polymerizable monomer, a polymerization initiator, and a dispersant, and is a polymerizable monomer.
  • the content is 50% by mass or more with respect to the total amount of the ink for inkjet recording, and the difference between the SP value of the polymerizable monomer and the SP value of the dispersant is 3.8 MPa 1/2 to 16.0 MPa 1/2 . be.
  • rings A and B each independently represent an aromatic or heteroaromatic ring
  • X A and X B each independently represent a monovalent substituent
  • GA and GB independently.
  • kA represents an integer from 0 to n A
  • kB represents an integer from 0 to n B
  • n A and n B are the largest of GA and GB that can be substituted with ring A or ring B , respectively.
  • Representing an integer that is a number X A and GA may be coupled to each other to form a ring
  • X B and GB may be coupled to each other to form a ring
  • GA and GB may be coupled to each other to form a ring, respectively.
  • the GAs and the GBs may be coupled to each other to form a ring structure.
  • Japanese Patent Application Laid-Open No. 2019-001983 describes an inkjet ink containing a squarylium dye, a dispersant, an organic solvent, and water.
  • the present inventors include a near-infrared absorbing dye represented by the formula 1, a polymerizable monomer, a polymerization initiator, and a dispersant, and the content of the polymerizable monomer is the total amount of the ink for inkjet recording.
  • the difference between the SP value of the polymerizable monomer and the SP value of the dispersant is 3.8 MPa 1/2 to 16.0 MPa 1/2 . It has been found that an image recording material having excellent readability can be obtained.
  • the reason why the ink according to the present disclosure can obtain an image recording material having excellent readability and readability after a lapse of time is presumed as follows.
  • the ink according to the present disclosure includes a near-infrared absorbing dye represented by the formula 1 and a dispersant.
  • a dispersant By adsorbing the dispersant on the surface of the near-infrared absorbing dye represented by the formula 1, the near-infrared absorbing dye represented by the formula 1 is dispersed in the ink. Since the surface of the near-infrared absorbing dye represented by the formula 1 is almost neutral, the dispersant is not easily adsorbed.
  • the present inventors have found that the compatibility between the dispersant and the dispersion medium contributes to the readability of the obtained image recording material.
  • the content of the polymerizable monomer is 50% by mass or more with respect to the total amount of the ink jet recording ink. Therefore, the present inventors have focused on the difference between the SP value of the polymerizable monomer, which occupies most of the ink according to the present disclosure, and the SP value of the dispersant as the dispersion medium.
  • the difference in SP value is 3.8 MPa 1/2 or more, it is estimated that the dispersant is difficult to be detached from the surface of the near-infrared absorbing dye represented by the formula 1 and the readability of the obtained image recording is improved. Will be done.
  • the dispersant adsorbed on the surface of the near-infrared absorbing dye represented by the formula 1 spreads appropriately, and the near-red represented by the formula 1 spreads appropriately. It is presumed that the externally absorbed dyes do not easily aggregate with each other. As a result, it is considered that the readability of the obtained image recorded matter is improved. Further, in the ink according to the present disclosure, the near-infrared absorbing dye represented by the formula 1 can be stably dispersed for a long time by a dispersant, and an image recorded material having excellent readability after a lapse of time can be obtained.
  • the ink according to the present disclosure contains a near-infrared absorbing dye represented by the formula 1.
  • the near-infrared absorbing dye represented by the formula 1 contained in the ink may be one kind or two or more kinds.
  • rings A and B each independently represent an aromatic ring or a heteroaromatic ring
  • X A and X B each independently represent a monovalent substituent
  • GA and GB are independent, respectively.
  • kA represents an integer of 0 to nA
  • kB represents an integer of 0 to nB.
  • nA represents the maximum integer in which GA can be replaced by ring A
  • nB represents the maximum integer in which GB can be replaced by ring B.
  • X A and GA may be bonded to each other to form a ring, and when a plurality of GA and GB are present, a plurality of GA , which are bonded to the ring A , may be formed . And a plurality of GBs bonded to the ring B may be bonded to each other to form a ring structure.
  • GA and GB each independently represent a monovalent substituent.
  • Examples of the monovalent substituent include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, -OR 10 , -COR 11 , and -COOR 12 .
  • R 10 to R 27 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
  • R 12 of -COOR 12 is a hydrogen atom (that is, a carboxy group)
  • the hydrogen atom may be dissociated (that is, a carbonate group) or may be in a salt state.
  • R 24 of —SO 2 OR 24 is a hydrogen atom (that is, a sulfo group)
  • the hydrogen atom may be dissociated (that is, a sulfonate group) or may be in a salt state.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
  • the alkenyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the carbon number of the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25.
  • the alkynyl group may be linear, branched, or cyclic, and is preferably linear or branched.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • the alkyl moiety of the aralkyl group is the same as the above alkyl group.
  • the aryl moiety of the aralkyl group is the same as the above aryl group.
  • the carbon number of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and even more preferably 7 to 25.
  • the heteroaryl group is preferably a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 8, and more preferably a monocyclic ring or a condensed ring having a condensed number of 2 to 4.
  • the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the heteroaryl group is preferably a 5-membered ring or a 6-membered ring.
  • the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • the heteroaryl group include a pyridine ring, a piperidine ring, a furan ring group, a flufuran ring, a thiophene ring, a pyrrole ring, a quinoline ring, a morpholine ring, an indole ring, an imidazole ring, a pyrazole ring, a carbazole ring, a phenothiazine ring, and a phenoxazine ring.
  • Examples thereof include an indole ring, a thiazole ring, a pyrazine ring, a thiadiazine ring, a benzoquinoline ring, and a thiazylazole ring.
  • alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, and heteroaryl group may have a substituent or may be unsubstituted.
  • substituents include the substituent described in paragraph No. 0030 of JP-A-2018-154672.
  • Substituents include an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group and an alkoxycarbonylamino group.
  • the substituents are an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an alkylthio group, an arylthio group and an aromatic hetero.
  • a ring thio group, a sulfonyl group, a hydroxy group, a mercapto group, a halogen atom, a cyano group, a sulfo group, or a carboxy group is preferable.
  • the "carbon number” of the substituent means the “total carbon number” of the substituent. Further, for the details of each substituent, the substituents described in paragraphs 0031 to 0035 of JP-A-2018-154672 can be referred to.
  • X A and X B each independently represent a monovalent substituent.
  • Substituents in X A and X B are preferably groups having active hydrogen, -OH, -SH, -COOH, -SO 3 H, -NR X1 R X2 , -NHCOR X1 , -CONR X1 R X2 , -NHCONR.
  • X1 R X2 , -NHCOOR X1 , -NHSO 2 R X1 , -B (OH) 2 or PO (OH) 2 are more preferred, and -OH, -SH or NR X1 R X 2 are even more preferred.
  • RX1 and RX2 independently represent a hydrogen atom or a monovalent substituent.
  • the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group. Of these, the substituent is preferably an alkyl group.
  • the alkyl group is preferably linear or branched. The details of the alkyl group, the alkenyl group, the alkynyl group, the aryl group, and the heteroaryl group are synonymous with the ranges described in GA and GB .
  • Ring A and ring B each independently represent an aromatic ring or a complex aromatic ring.
  • the aromatic ring and the complex aromatic ring may be a monocyclic ring or a condensed ring.
  • Examples of the aromatic ring and the heteroaromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an inden ring, an azulene ring, a heptalene ring, an indecene ring, a perylene ring, a pentacene ring, an acetaphthalene ring, a phenanthrene ring, an anthracene ring, and a naphthalene ring.
  • the ring A and the ring B are preferably aromatic rings, more preferably benzene rings or naphthalene rings.
  • the aromatic ring may be unsubstituted or may have a substituent.
  • substituents described in GA and GB include the substituents described in GA and GB .
  • X A and GA , X B and GB may be bonded to each other to form a ring, and when a plurality of GA and GB are present, they may be bonded to each other to form a ring.
  • the ring is preferably a 5-membered ring or a 6-membered ring.
  • the ring may be a single ring or a double ring.
  • Rings may be formed by bonding via a divalent linking group selected from the group consisting of -O-, -NH-, -BR- and combinations thereof. It is preferable that X A and GA, X B and GB, GA and GB are bonded to each other via -BR- to form a ring.
  • R represents a hydrogen atom or a monovalent substituent.
  • substituents described in GA and GB include the substituents described in GA and GB , and an alkyl group or an aryl group is preferable.
  • kA represents an integer from 0 to nA
  • kB represents an integer from 0 to nB
  • nA represents the maximum integer substitutable for the A ring
  • nB represents the maximum integer substitutable for the B ring.
  • kA and kB For kA and kB, 0 to 4 is preferable, 0 to 2 is more preferable, and 0 to 1 is particularly preferable, respectively. Further, it is preferable not to include the case where kA and kB simultaneously represent 0 (zero).
  • the near-infrared absorbing dye represented by the formula 1 is preferably a compound represented by the following formula 2 from the viewpoint of light resistance.
  • R 1 and R 2 each independently represent a monovalent substituent.
  • R 3 and R 4 each independently represent a hydrogen atom or an alkyl group.
  • X 1 and X 2 independently represent an oxygen atom or -N (R 5 )-.
  • R 5 represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • X 3 and X 4 independently represent a carbon atom or a boron atom, respectively.
  • t and u represent 1 when X 3 and X 4 are boron atoms, and represent 2 when X 3 and X 4 are carbon atoms.
  • Y 1 , Y 2 , Y 3 and Y 4 each independently represent a monovalent substituent.
  • Y 1 and Y 2 and Y 3 and Y 4 may be coupled to each other to form a ring.
  • a plurality of Y 1 , Y 2 , Y 3 and Y 4 are present, they may be bonded to each other to form a ring.
  • p and s each independently represent an integer of 0 to 3
  • q and r each independently represent an integer of 0 to 2.
  • R 1 and R 2 may be the same or different, but are preferably the same. Further, when t and u are 2 , the two R1s and the two R2s may be the same or different, but are preferably the same.
  • Examples of the monovalent substituent represented by R 1 and R 2 include monovalent substituents similar to GA and GB. Of these, R 1 and R 2 are preferably aryl groups.
  • the aryl group may have a monovalent substituent or may be unsubstituted.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 14 carbon atoms.
  • Examples of the monovalent substituent represented by Y 1 , Y 2 , Y 3 and Y 4 include monovalent substituents similar to GA and GB .
  • X 1 and X 2 may be the same or different, but are preferably the same.
  • X 1 and X 2 are preferably ⁇ N ( R5) ⁇ .
  • the alkyl group, aryl group and heteroaryl group represented by R5 may be unsubstituted or have a monovalent substituent.
  • Examples of the monovalent substituent include monovalent substituents similar to GA and GB .
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 4, and particularly preferably 1 to 2.
  • the alkyl group may be linear or branched.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • the heteroaryl group may be monocyclic or polycyclic.
  • the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
  • the hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
  • R 5 is preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • X 3 and X 4 may be the same or different, but are preferably the same. It is preferable that X 3 and X 4 are boron atoms.
  • the number of carbon atoms of the alkyl group represented by R 3 and R 4 is preferably 1 to 4, and more preferably 1 or 2.
  • the alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • R 3 and R 4 are each independently preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • the molecular weight of the near-infrared absorbing dye represented by the formula 1 is preferably 100 to 2,000, more preferably 150 to 1,000.
  • the near-infrared absorption dye represented by the formula 1 is described in detail in JP-A-2011-2008101, and the compound described here can be suitably used as the squarylium dye in the present disclosure.
  • the near-infrared absorbing dye represented by the formula 1 and the near-infrared absorbing dye represented by the formula 2 may be tautomers thereof.
  • the tautomer can be referred to, for example, in paragraph 0034 of WO 2016-136783.
  • the near-infrared absorbing dye represented by the formula 1 includes Specific Examples B-1, B-3, B-7, B-37, B-41, and B. -42, B-43, B-44, or B-45 is preferable.
  • the near-infrared absorbing dye represented by the formula 1 is preferably dispersed in the ink in the form of particles.
  • the volume average particle size of the near-infrared absorbing dye represented by the formula 1 is preferably 10 nm or more, more preferably 15 nm or more, further preferably 20 nm or more, and particularly preferably 50 nm or more.
  • the volume average particle size of the near-infrared absorbing dye represented by the formula 1 is preferably 400 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, from the viewpoint of dispersibility and ejection property.
  • the volume average particle size of the near-infrared absorbing dye refers to the volume average particle size in the coated state when the near-infrared absorbing dye is coated with a dispersant or the like.
  • the volume average particle size can be measured by a dynamic light scattering method using a Zetasizer Nano ZS (manufactured by Malvern Panasonic) as a measuring device.
  • the near-infrared absorbing dye is preferably dispersed using a disperser.
  • the disperser include a circulating bead mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill and a paint shaker.
  • the content of the near-infrared absorbing dye represented by the formula 1 is preferably 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and 0. 3% by mass to 7% by mass is more preferable.
  • the ink according to the present disclosure contains a polymerizable monomer.
  • the polymerizable monomer contained in the ink may be one kind or two or more kinds.
  • the monomer means a compound having a molecular weight of less than 1000.
  • the polymerizable monomer is a compound having a polymerizable group and having a molecular weight of less than 1000.
  • the molecular weight of the polymerizable monomer is preferably 100 or more and less than 1000, more preferably 100 to 800, and even more preferably 150 to 700.
  • the molecular weight of the polymerizable monomer is calculated from the type and number of atoms constituting the polymerizable monomer.
  • Examples of the polymerizable monomer include a photopolymerizable monomer in which the polymerization reaction proceeds by irradiation with light, and a heat-polymerizable monomer in which the polymerization reaction proceeds by heating or irradiation with infrared rays.
  • Examples of the photopolymerizable monomer include a polymerizable monomer having a radically polymerizable group (that is, a radically polymerizable monomer) and a polymerizable monomer having a cationically polymerizable cationically polymerizable group (that is, a cationically polymerizable monomer). ).
  • the polymerizable monomer is preferably a photopolymerizable monomer, and more preferably a radically polymerizable monomer.
  • the radically polymerizable monomer is preferably an ethylenically unsaturated monomer having an ethylenically unsaturated group.
  • examples of the ethylenically unsaturated monomer include a monofunctional ethylenically unsaturated monomer and a polyfunctional ethylenically unsaturated monomer.
  • the monofunctional ethylenically unsaturated monomer is a monomer having one ethylenically unsaturated group, and is, for example, a monofunctional (meth) acrylate, a monofunctional (meth) acrylamide, a monofunctional aromatic vinyl compound, a monofunctional vinyl ether and the like. Examples include monofunctional N-vinyl compounds.
  • Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • Examples of the monofunctional (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and Nn-butyl (meth) acrylamide.
  • Examples include (meth) acrylamide and (meth) acryloylmorpholin.
  • Examples of the monofunctional aromatic vinyl compound include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, and 3-methyl.
  • Styrene 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene,3-octyl Styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, octenyl styrene, 4-t-butoxycarbonyl styrene and 4- Included is t-butoxystyrene.
  • Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether and 4-methyl.
  • Examples of the monofunctional N-vinyl compound include N-vinyl- ⁇ -caprolactam and N-vinylpyrrolidone.
  • the monofunctional ethylenically unsaturated compound is preferably a compound having a ring structure from the viewpoint of improving curability.
  • Examples of the monofunctional ethylenically unsaturated compound having a ring structure include cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, and bornyl (meth) acrylate.
  • the polyfunctional ethylenically unsaturated monomer is a monomer having two or more ethylenically unsaturated groups, and examples thereof include polyfunctional (meth) acrylate and polyfunctional vinyl ether.
  • polyfunctional (meth) acrylate examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol di (meth).
  • polyfunctional vinyl ether examples include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, and hexanediol di.
  • the polyfunctional ethylenically unsaturated monomer is preferably a compound having oxygen atoms from the viewpoint of improving curability, and the ratio of the number of oxygen atoms to the number of carbon atoms contained in one molecule is 0.2 or more. Is preferable, and 0.3 or more is more preferable. The upper limit of the ratio is not particularly limited, but is, for example, 0.5. Examples of the compound in which the ratio of the number of oxygen atoms to the number of carbon atoms contained in one molecule is 0.2 or more include polyethylene glycol diacrylate.
  • the polymerizable monomers are described by Shinzo Yamashita, "Handbook of Crosslinking Agents” (1981, Taiseisha); Kiyomi Kato, “UV / EB Curing Handbook (Raw Materials)” (1985, Polymer Publishing Association); Ed., Radtech Study Group, “Application and Market of UV / EB Curing Technology", p. 79, (1989, CMC); Eiichiro Takiyama, "Polyester Resin Handbook", (1988, Nikkan Kogyo Shimbun), etc. It may be a commercially available product of.
  • the ink according to the present disclosure preferably contains a polyfunctional polymerizable monomer as the polymerizable monomer, and more preferably contains a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer.
  • a polyfunctional polymerizable monomer as the polymerizable monomer, and more preferably contains a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer.
  • the polyfunctional polymerizable monomer in the ink it is possible to record an image having excellent curability.
  • the polyfunctional polymerizable monomer in the ink it is possible to suppress the phenomenon (so-called migration) in which the unreacted polymerizable monomer is transferred to the outside from the image recording material.
  • it is excellent in that it can be applied to packaging materials in the food packaging field and the cosmetic packaging field where the safety of the base material is strictly required.
  • the ratio of the polyfunctional polymerizable monomer to the polymerizable monomer contained in the ink is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of curability. Further, the upper limit of the ratio of the polyfunctional polymerizable monomer to the polymerizable monomer contained in the ink is not particularly limited and may be 100% by mass.
  • the polymerizable monomer preferably has a glass transition temperature (Tg) of 30 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of improving readability and solvent resistance after the scraping test. preferable.
  • Tg glass transition temperature
  • the proportion of the polymerizable monomer having a glass transition temperature of 30 ° C. or higher in the polymerizable monomer is preferably 90% by mass or more, and more preferably 92% by mass or more.
  • the upper limit of the above ratio is not particularly limited, and is, for example, 100% by mass.
  • the proportion of the polymerizable monomer having a glass transition temperature of 30 ° C. or higher in the polymerizable monomer is 90% by mass or more, the readability after the scraping test is further improved.
  • the polymerizable monomer having a Tg of 30 ° C. or higher include isobornyl (meth) acrylate (Tg: 97 ° C.).
  • the glass transition temperature (Tg) of the polymerizable monomer means the glass transition temperature when the polymerizable monomer is a homopolymer. Any polymerization initiator is added to the polymerizable monomer to obtain a homopolymer having a weight average molecular weight of 10,000 to 20,000.
  • the glass transition temperature (Tg) of a homopolymer having a weight average molecular weight of 10,000 to 20,000 is adopted as the glass transition temperature of the polymerizable monomer.
  • the glass transition temperature (Tg) of the homopolymer varies depending on the weight average molecular weight, but in the range of the weight average molecular weight of 10,000 to 20,000, the fluctuation of Tg due to the difference in the weight average molecular weight is negligible.
  • the weight average molecular weight means a value measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • HLC registered trademark
  • TSKgel registered trademark
  • Super Multipore HZ-H 4.6 mm ID x 15 cm, manufactured by Tosoh Co., Ltd.
  • THF tetrahydrofuran
  • the measurement is performed using an RI detector with a sample concentration of 0.45% by mass, a flow rate of 0.35 ml / min, a sample injection amount of 10 ⁇ l, and a measurement temperature of 40 ° C.
  • the calibration curve is "Standard sample TSK standard, polystyrene” manufactured by Tosoh Co., Ltd .: "F-40", “F-20”, “F-4", “F-1”, “A-5000”, “A-” It is made from 8 samples of "2500”, “A-1000", and "n-propylbenzene".
  • the glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) in accordance with ASTMD3418-8.
  • DSC differential scanning calorimeter
  • the glass transition temperature (Tg) is measured under normal measurement conditions using a differential scanning calorimeter (product name "EXSTAR6220") manufactured by SII Nanotechnology.
  • the content of the polymerizable monomer is 50% by mass or more, more preferably 60% by mass to 95% by mass, and further preferably 70% by mass to 90% by mass with respect to the total amount of the ink.
  • the content of the polymerizable monomer is 50% by mass or more, the obtained image recording material is excellent in readability.
  • the SP value of the polymerizable monomer is not particularly limited as long as the difference between the SP value of the polymerizable monomer and the SP value of the dispersant described later is 3.8 MPa 1/2 to 16.0 MPa 1/2 .
  • the SP value of the polymerizable monomer is preferably 15.0 MPa 1/2 to 30.0 MPa 1/2 , and 17.0 MPa 1/2 to 20.0 MPa 1/2 , from the viewpoint of curability and dispersion stability. Is more preferable.
  • the SP value of the polymerizable monomer means the Hansen solubility parameter.
  • the Hansen solubility parameter is a three-dimensional space obtained by dividing the solubility parameter introduced by Hildebrand into three components, a dispersion term ⁇ d, a polarity term ⁇ p, and a hydrogen bond term ⁇ h. ..
  • the SP value ⁇ of the polymerizable monomer is a value calculated using the following formula A.
  • SP value ( ⁇ ) [MPa 1/2 ] ( ⁇ d 2 + ⁇ p 2 + ⁇ h 2 ) 1/2 ... (A)
  • the dispersion term ⁇ d, the polarity term ⁇ p, and the hydrogen bond term ⁇ h are calculated using HSPiP (version 4.1.07) software.
  • MPDDA (3-methyl-1,5-pentanediol diacrylate), DPGDA (dipropylene glycol diacrylate), IBOA (isobornyl acrylate), TCDDMDA (tricyclodecanedimethanol dimethacrylate), TMPTA (trimethylolpropane tri)
  • Table 1 shows the dispersion term ⁇ d, polar term ⁇ p, hydrogen bond term ⁇ h, and SP value of ACMO (acryloylmorpholine), EOTMPTA (trimethylolpropane EO-added triacrylate), and PEA (phenoxyethyl acrylate). ..
  • the SP value of the polymerizable monomers is calculated by using the following method. First, the weighted average values of the dispersion term, the polarity term, and the hydrogen bond term of the polymerizable monomer contained in the ink are calculated as ⁇ d, ⁇ p, and ⁇ h. Then, based on the calculated ⁇ d, ⁇ p, and ⁇ h, the SP value is calculated using the above formula A.
  • ⁇ d is calculated using the following formula B1.
  • ⁇ dm represents the dispersion term of the polymerizable monomer of the m item (m represents an integer of 1 or more) in the polymerizable monomer
  • W m represents the dispersion term of the polymerizable monomer of the m item in the ink. Represents the content ratio (mass%) with respect to the total amount.
  • ⁇ d ⁇ d m W m / ⁇ W m ... (B1)
  • ⁇ p and ⁇ h are calculated by the following formulas B2 and B3.
  • ⁇ p ⁇ p m W m / ⁇ W m ... (B2)
  • ⁇ h ⁇ h m W m / ⁇ W m ... (B3)
  • ⁇ pm represents the polarity term of the polymerizable monomer of the m item (m represents an integer of 1 or more) in the polymerizable monomer.
  • ⁇ h m represents the hydrogen bond term of the polymerizable monomer of the m item (m represents an integer of 1 or more) in the polymerizable monomer.
  • the ink according to the present disclosure contains a dispersant.
  • the dispersant has a function of dispersing the squarylium dye represented by the formula 1.
  • the weight average molecular weight of the dispersant is preferably 100,000 or less, more preferably 75,000 or less, and even more preferably 50,000 or less.
  • the weight average molecular weight of the dispersant is preferably 1000 or more, more preferably 2000 or more, and even more preferably 3000 or more.
  • the weight average molecular weight of the dispersant is 100,000 or less, the diffusion rate of the dispersant in the dispersion medium is improved, so that an image recording material having excellent readability can be obtained.
  • the weight average molecular weight of the dispersant is 1000 or more, the compatibility with the dispersion medium does not become too high, and the near-infrared absorbing dye represented by the formula 1 can be stably dispersed by the dispersant.
  • Weight average molecular weight means a value measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • HLC registered trademark
  • -8020GPC manufactured by Tosoh Corporation
  • TSKgel registered trademark
  • Super Multipore HZ-H 4.6 mm ID x 15 cm
  • THF tetrahydrofuran
  • the measurement is performed using an RI detector with a sample concentration of 0.45% by mass, a flow rate of 0.35 ml / min, a sample injection amount of 10 ⁇ l, and a measurement temperature of 40 ° C.
  • the calibration curve is "Standard sample TSK standard, polystyrene” manufactured by Tosoh Co., Ltd .: “F-40", “F-20”, “F-4", “F-1”, "A-5000", "A-” It is made from 8 samples of "2500", "A-1000", and "n-propylbenzene".
  • the dispersant is preferably a polymer, and the polymer may be any of a random polymer, a block polymer, and a graft polymer.
  • the dispersant is preferably a block polymer from the viewpoint of readability after a lapse of time.
  • the block polymer has, for example, an adsorption block having an adsorbing group adsorbing to the near-infrared absorbing dye represented by the formula 1 and a dispersion medium-affinitive block having a functional group compatible with the dispersion medium. Since the block polymer has a low shielding property of the adsorbent group and a high motility, the adsorption rate to the near-infrared absorbing dye represented by the formula 1 is high. Therefore, when the dispersant is a block polymer, the readability is further improved.
  • the adsorbing groups are gathered, the adsorbing power to the near-infrared absorbing dye represented by the formula 1 is high. Therefore, when the dispersant is a block polymer, the readability after aging is further improved.
  • the dispersant preferably has a basic functional group or an acidic functional group.
  • a dispersant having a basic functional group and a pigment derivative having an acidic functional group are combined, or a dispersant having an acidic functional group and a basic functional group are used.
  • the combination with the pigment derivative to have is preferable.
  • the pigment derivative is easily adsorbed on the dispersant due to the acid-base interaction. Due to the steric repulsion between the dispersants, the near-infrared absorbing dye represented by the formula 1 can be stably dispersed in the ink, and the stability over time is improved. As a result, the readability after a lapse of time is improved.
  • Examples of the basic functional group include an amino group, an amide group and an imino group.
  • the dispersant may have only one type of basic functional group, or may have two or more types.
  • the acidic functional group examples include a carboxy group and a sulfo group.
  • the dispersant may have only one type of acidic functional group, or may have two or more types.
  • the basic value of the dispersant is preferably 15 mgKOH / g or more, and 20 mgKOH / g, from the viewpoint of improving readability and readability after a lapse of time.
  • the above is more preferable, and 25 mgKOH / g or more is further preferable.
  • the upper limit of the base value of the dispersant is not particularly limited, but is, for example, 40 mgKOH / g.
  • the base value is a value measured by the perchloric acid method specified by JIS K 2501: 2003.
  • the base value is obtained as the number of milligrams (mg) of hydrochloric acid or perchloric acid equivalent to potassium hydroxide required to neutralize all the basic components contained in 1 g of the sample.
  • the acid value of the dispersant is preferably 15 mgKOH / g or more, preferably 20 mgKOH / g or more, from the viewpoint of improving readability and readability over time. Is more preferable, and 25 mgKOH / g or more is further preferable.
  • the upper limit of the acid value of the dispersant is not particularly limited, but is, for example, 40 mgKOH / g.
  • the acid value is a value measured by the method described in JIS K0070: 1992.
  • the acid value is obtained as the number of milligrams (mg) of potassium hydroxide required to neutralize the totally acidic component contained in 1 g of the sample.
  • the dispersant may be a commercially available product.
  • commercially available products include SOLSERSE® series (eg, SOLSERSE 16000, 21000, 32000, 35000, 41000, 41090, 43000, 44000, 46000, 54000, 55000, 71000, etc.) of Loubrizole.
  • DISPERBYK® series (eg DISPERBYK 102, 110, 111, 118, 170, 190, 194N, 2001, 2013, 2015, 2090, 2096, etc.), Evonik's TEGO® Dispers series (eg TEGO) Dispers 610, 610S, 630, 651, 655, 750W, 755W, etc.), Kusumoto Kaseisha's Disparon (registered trademark) series (eg DA-375, DA-1200, etc.), Kyoei Chemical Industry Co., Ltd.
  • Floren series eg: WK-13E, G-700, G-900, GW-1500, GW-1640, WK-13E, etc.
  • BASF's EFKA (registered trademark) series eg, EFKA PX 4701, EFKA PX 4731, EFKA PX 4732, etc.
  • the content of the dispersant is preferably 0.7% by mass to 5% by mass, and 0.8% by mass to 4% by mass, based on the total amount of the ink, from the viewpoint of improving readability and readability after a lapse of time. % Is more preferable.
  • the ratio of the content of the dispersant to the content of the near-infrared absorbing dye represented by the formula 1 is preferably 0.1 to 20 and more preferably 0.2 to 5 on a mass basis. It is more preferably 0.5 to 5.
  • the SP value of the dispersant is not particularly limited as long as the difference between the SP value of the polymerizable monomer and the SP value of the dispersant is 3.8 MPa 1/2 to 16.0 MPa 1/2 .
  • the SP value of the dispersant is preferably 21 MPa 1/2 to 34 MPa 1/2 , more preferably 24 MPa 1/2 to 34 MPa 1/2 , from the viewpoint of dispersion stability.
  • the SP value of the dispersant is, for example, the following K.I. W. SUH, J.M. M. It is calculated using the formula of CORBETT (Journal of Applied Polymer Science, 12, 2359, 1968).
  • SP value ⁇ (V ml ) 1/2 ⁇ ⁇ H + (V mh ) 1/2 ⁇ ⁇ D ⁇ / ⁇ (V ml ) 1/2 + (V mh ) 1/2 ⁇ V ml , V mh , ⁇ H, and ⁇ D are quantified drops at the turbidity point when n-hexane is added to 0.5 g (solid content) of the dispersant dissolved in 10 mL of a good solvent at a measurement temperature of 20 ° C.
  • V ml (Molecular content of good solvent) ⁇ (Molecular content of n-hexane) / ⁇ (1- VH ) ⁇ (Molecular content of n-hexane) + VH ⁇ (Molecular content of good solvent) ⁇
  • V mh (Molecular content of good solvent) ⁇ (Molecular content of deionized water) / ⁇ (1-V D ) ⁇ (Molecular content of deionized water) + V D ⁇ (Molecular content of good solvent) ⁇
  • V H H / (10 + H)
  • the molecular content of n-hexane is 130.3 mL / mol,
  • the SP value of n-hexane is 7.27 (cal / cm 3 ) 1/2
  • the SP value of deionized water is 23.39 (cal / cm 3 ) 1/2
  • the good solvent used to dissolve the dispersant is not particularly limited as long as it is a solvent capable of dissolving the dispersant, and can be appropriately selected.
  • the good solvent include acetone.
  • the molecular content of acetone is 74.4 mL / mol
  • the SP value of acetone is 9.72 (cal / cm 3 ) 1/2 .
  • the SP value of each solvent is a value calculated using HSPiP (version 4.1.07) software.
  • the molecular weight (mL / mol) of each solvent is a value obtained by dividing the molecular weight (g / mol) by the density (g / mL).
  • the unit of the obtained SP value is (cal / cm 3 ) 1/2 . Based on the fact that 1 (cal / cm 3 ) 1/2 ⁇ 2.05 MPa 1/2 , the unit can be converted from (cal / cm 3 ) 1/2 to MPa 1/2 .
  • the difference between the SP value of the polymerizable monomer and the SP value of the dispersant is 3.8 MPa 1/2 to 16.0 MPa 1/2 .
  • the above difference means the absolute value of the value obtained by subtracting the SP value of the other from the SP value of one.
  • the dispersant When the difference in SP value is 3.8 MPa 1/2 or more, the dispersant is difficult to desorb from the surface of the near-infrared absorbing dye represented by the formula 1, and the near-infrared absorbing dye represented by the formula 1 is difficult to desorb. It is estimated that the dispersion stability is improved.
  • the difference in the SP value is 16.0 MPa 1/2 or less, the dispersant adsorbed on the surface of the near-infrared absorbing dye represented by the formula 1 spreads appropriately, and the near-red represented by the formula 1 spreads appropriately. It is presumed that the externally absorbed dyes do not easily aggregate with each other. As a result, an image recorded material having excellent readability can be obtained.
  • the near-infrared absorbing dye represented by the formula 1 can be stably dispersed for a long time by a dispersant, and an image recorded material having excellent readability after a lapse of time can be obtained.
  • the difference in the SP value is preferably 4.5 MPa 1/2 to 15.5 MPa 1/2 , and 5.0 MPa 1/2 to 15.2 MPa from the viewpoint of improving readability and readability after a lapse of time. It is more preferably 1/2 .
  • the ink according to the present disclosure preferably further contains a pigment derivative.
  • a pigment derivative is a compound having a structure derived from a pigment in the molecule and having a molecular weight of less than 1000.
  • the ink contains a pigment derivative
  • a ⁇ - ⁇ interaction acts between the pigment derivative and the near-infrared absorbing dye represented by the formula 1, and the acid-base interaction between the pigment derivative and the dispersant.
  • the action works. Therefore, the near-infrared absorbing dye represented by the formula 1 is more stably dispersed by the dispersant, and the stability of the ink with time is improved. As a result, the readability after a lapse of time is improved.
  • the pigment derivative preferably has a basic functional group or an acidic functional group.
  • the basic functional group examples include an amino group, an amide group and an imino group.
  • the pigment derivative may have only one type of basic functional group, or may have two or more types.
  • the acidic functional group examples include a carboxy group and a sulfo group.
  • the pigment derivative may have only one type of acidic functional group, or may have two or more types.
  • the pigment derivative having an acidic functional group is preferably represented by the following formula 3. P- [R 10 -X 10 ] m ... (3)
  • P represents a dye residue
  • R 10 represents a divalent linking group
  • X 10 independently represents a carboxy group or a sulfo group.
  • m represents the maximum integer that can be replaced with P.
  • P examples include diketopyrrolopyrrole dyes; azo dyes such as azo, disazo, and polyazo; phthalocyanine dyes; anthraquinones such as diaminodianthraquinone, anthrapyrimidine, flavantron, anthraquinone, indantron, pyratron, and biolantron. Residues of quinacridone dyes; dioxazine dyes; perinone dyes; perylene dyes; thioindigo dyes; isoindoline dyes; isoindrinone dyes; quinophthalone dyes; slene dyes and metal complex dyes Can be mentioned.
  • P is preferably a residue of diketopyrrolopyrrole dye, phthalocyanine dye, anthraquinone dye or dioxazine dye from the viewpoint of improving readability and readability over time, and is preferably diketopyrrolopyrrole. More preferably, it is a dye, a phthalocyanine dye or an anthraquinone dye.
  • R 30 represents a hydrogen atom or an alkyl group.
  • R 10 is preferably a single bond.
  • X 10 is preferably a sulfo group.
  • the plurality of X10s may be the same or different, but are preferably the same.
  • [M] m is preferably 1 to 10, preferably 1 to 5, and more preferably 1 to 3.
  • the pigment derivative contained in the ink may be one kind or two or more kinds.
  • the content of the pigment derivative is preferably 0.005% by mass to 0.1% by mass with respect to the total amount of the ink from the viewpoint of improving readability and readability after a lapse of time.
  • the content of the pigment derivative is 0.12% by mass to 15% by mass with respect to the total amount of the near-infrared absorbing dye represented by the formula 1 from the viewpoint of improving the readability and the readability after a lapse of time. It is preferably 0.15% by mass to 12% by mass, and more preferably 0.15% by mass to 12% by mass.
  • the ink according to the present disclosure preferably contains a polymerization initiator.
  • the polymerization initiator contained in the ink may be one kind or two or more kinds.
  • the polymerization initiator is preferably a radical polymerization initiator.
  • radical polymerization initiator examples include alkylphenone compounds, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, and activities.
  • examples thereof include ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
  • the polymerization initiator is preferably at least one selected from the group consisting of an acylphosphine compound and a thio compound, and is preferably at least one selected from the group consisting of an acylphosphine oxide compound and a thioxanthone compound. It is preferable to include an acylphosphine oxide compound and a thioxanthone compound.
  • the readability after the transfer test and the readability after the scraping test are improved.
  • acylphosphine oxide compound examples include a monoacylphosphine oxide compound and a bisacylphosphine oxide compound, and a bisacylphosphine oxide compound is preferable.
  • Examples of the monoacylphosphine oxide compound include isobutyryldiphenylphosphine oxide, 2-ethylhexanoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and (2,4,6-trimethylbenzoyl) ethoxyphenyl.
  • Phosphine oxide o-toluyldiphenylphosphine oxide, pt-butylbenzoyldiphenylphosphine oxide, 3-pyridylcarbonyldiphenylphosphine oxide, acryloyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, pivaloylphenylphosphine acid vinyl ester, adipoilbis Diphenylphosphine oxide, pivaloyldiphenylphosphine oxide, p-toluyldiphenylphosphine oxide, 4- (t-butyl) benzoyldiphenylphosphine oxide, terephthaloylbisdiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, versatoyldiphenylphosphine oxide
  • oxides 2-methyl-2-ethylhexanoyldiphenylphosphine
  • bisacylphosphine oxide compound examples include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6-dichlorobenzoyl).
  • the acylphosphine oxide compounds are bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (product name "Omnirad 819", manufactured by IGM Resins VV), 2,4,6-trimethylbenzoyldiphenylphosphine.
  • Oxide product name "Omnirad TPO H", manufactured by IGM Resins B.V.
  • (2,4,6-trimethylbenzoyl) ethoxyphenylphosphine oxide product name "Omnirad TPO-L", IGM Resins B.V.
  • thioxanthone compound examples include thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-.
  • the thioxanthone compound may be a commercially available product.
  • commercially available products include SPEEDCURE series manufactured by Rambson (eg, SPEEDCURE 7010, SPEEDCURE CPTX, SPEEDCURE ITX, etc.).
  • the ratio of the content of the acylphosphine oxide compound to the content of the thioxanthone compound is preferably 2 to 10 on a mass basis, preferably 3 to 7. It is more preferable to have.
  • the content of the polymerization initiator is preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total amount of the ink, from the viewpoint of improving readability and readability after a lapse of time.
  • the upper limit of the content of the polymerization initiator is not particularly limited, but is, for example, 30% by mass.
  • the content of the acylphosphine oxide compound is 5% by mass to 15% by mass with respect to the total amount of the ink from the viewpoint of improving readability and readability over time. It is preferably 8% by mass to 12% by mass, and more preferably 8% by mass to 12% by mass.
  • the content of the thioxanthone compound is 0.5% by mass to 5% by mass based on the total amount of the ink from the viewpoint of improving the readability after the transfer test and the readability after the scraping test. It is preferably by mass%, more preferably 1% by mass to 3% by mass.
  • the ink according to the present disclosure may further contain the following other components.
  • the ink according to the present disclosure preferably contains at least one siloxane compound.
  • the siloxane compound acts as a surfactant in the ink.
  • the siloxane compound tends to be unevenly distributed near the interface of the ink film with air when the ink is cured. This improves readability after the scraping test.
  • the siloxane compound is preferably an organically modified polysiloxane.
  • the organically modified polysiloxane refers to a polysiloxane in which an organic group is introduced into a part of the methyl group of the polydimethylsiloxane. The position where the organic group is introduced may be the terminal of polydimethylsiloxane or the side chain.
  • organically modified polysiloxane examples include polyether-modified polydimethylsiloxane, phenyl-modified polydimethylsiloxane, alcohol-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane, aralkyl-modified polydimethylsiloxane, fatty acid ester-modified polydimethylsiloxane, and epoxy-modified polysiloxane.
  • examples thereof include dimethylsiloxane, amine-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, and mercapto-modified polydimethylsiloxane.
  • the siloxane compound preferably contains a siloxane compound having a polymerizable group.
  • the siloxane compound having a polymerizable group tends to be unevenly distributed near the interface of the ink film with air when the ink is cured. ..
  • the readability after the adhesion test and the readability after the transfer test are improved.
  • the molecular weight of the siloxane compound having a polymerizable group is 1000 or more, and it is distinguished from the polymerizable monomer.
  • the number of polymerizable groups contained in the siloxane compound is not particularly limited, and is, for example, 1 to 5.
  • the polymerizable group of the siloxane compound is preferably the same as the polymerizable group of the polymerizable monomer contained in the ink.
  • the polymerizable group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group, and even more preferably a (meth) acryloyl group.
  • the siloxane compound having a polymerizable group is preferably an organically modified polysiloxane having an organic group containing a polymerizable group introduced therein.
  • the siloxane compound having a polymerizable group may be a commercially available product.
  • Examples of commercially available products include TEGORAD 2100 manufactured by Evonik Industries, Inc.
  • the content of the siloxane compound is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass, based on the total amount of the ink. , 0.05% by mass to 1.5% by mass is more preferable.
  • the content of the siloxane compound having a polymerizable group is preferably 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass, based on the total amount of the ink.
  • an image recorded material having excellent readability can be obtained.
  • the content of the siloxane compound is 0.1% by mass or more, the polymerization of the ink film near the interface with air is promoted, and the readability after the adhesion test and the readability after the transfer test are improved. ..
  • the ink according to the present disclosure preferably contains a polymerization inhibitor.
  • the polymerization inhibitor contained in the ink may be one kind or two or more kinds.
  • polymerization inhibitor examples include hydroquinone compounds, phenothiazines, catechols, alkylphenols, alkylbisphenols, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionic acid ester, and mercaptobenzimidazole. , Phosphites, nitrosoamine compounds, hinderedamine compounds, and nitroxyl radicals.
  • the polymerization inhibitor is preferably at least one selected from the group consisting of a nitrosamine compound, a hindered amine compound, a hydroquinone compound and a nitroxyl radical, and is preferably selected from the group consisting of a nitrosoamine compound, a hydroquinone compound and a nitroxyl radical. It is more preferable that the compound is at least one, and further preferably contains a nitrosoamine compound, a hydroquinone compound and a nitroxyl radical.
  • nitrosamine compound examples include N-nitroso-N-phenylhydroxylamine aluminum salt and N-nitroso-N-phenylhydroxylamine. Above all, the nitrosamine compound is preferably an N-nitrosamine-N-phenylhydroxylamine aluminum salt.
  • the hindered amine compound is a compound having a hindered amine structure in the molecule.
  • the hindered amine compound include compounds described in JP-A-61-91257.
  • the hindered amine compound is preferably a derivative of 2,2,6,6-tetramethylpiperidine having a structure in which all hydrogens on the carbons at the 2- and 6-positions of piperidine are substituted with methyl groups.
  • the hindered amine compound include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and 1- (3,5-di-tert-butyl-4-hydroxyphenylpropionyloxyethyl) -4- (3). , 5-Di-tert-butyl-4-hydroxyphenylpropionyloxy) -2,2,6,6-tetramethylpiperidine.
  • hydroquinone compound examples include hydroquinone, methylhydroquinone, t-butylhydroquinone, and p-methoxyphenol. Above all, the hydroquinone compound is preferably p-methoxyphenol.
  • nitroxyl radical examples include 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL). Can be mentioned. Above all, the nitroxyl radical is preferably 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (TEMPOL).
  • the content of the polymerization inhibitor is preferably 1% by mass or more, more preferably 1.5% by mass or more, based on the total amount of the ink, from the viewpoint of improving the stability of the ink over time.
  • the upper limit of the content of the polymerization inhibitor is not particularly limited, but is preferably 5% by mass from the viewpoint of polymerizability.
  • the content of the nitrosamine compound is preferably 0.5% by mass to 5% by mass, preferably 0% by mass, based on the total amount of the ink, from the viewpoint of improving the stability of the ink over time. It is more preferably 5.5% by mass to 2% by mass.
  • the content of the hydroquinone compound is preferably 0.1% by mass to 5% by mass, preferably 0% by mass, based on the total amount of the ink, from the viewpoint of improving the stability of the ink over time. It is more preferably 5.5% by mass to 2% by mass.
  • a sensitizer When the ink according to the present disclosure contains a photopolymerization initiator, a sensitizer may be contained together with the photopolymerization initiator. When the ink contains a sensitizer, the curability is improved, and particularly when an LED light source is used, the curability is improved. The sensitizer also contributes to improving the light resistance of the ink.
  • a sensitizer is a substance that absorbs a specific active energy ray and becomes an electronically excited state.
  • the sensitizer in the electron-excited state comes into contact with the photopolymerization initiator and causes actions such as electron transfer, energy transfer, and heat generation. This promotes a chemical change in the photopolymerization initiator.
  • sensitizer examples include ethyl 4- (dimethylamino) benzoate (EDB), anthraquinone, 3-acylcoumarin derivative, terphenyl, styryl ketone, 3- (aloylmethylene) thiazolin, succinoquinone, eosin, and rhodamine.
  • Eosin a compound represented by the general formula (i) described in JP-A-2010-24276, and a compound represented by the general formula (I) described in JP-A-6-107718.
  • the content of the sensitizer is preferably 1.0% by mass to 15.0% by mass, and 1.5% by mass to 10. It is more preferably 0% by mass, and even more preferably 2.0% by mass to 6.0% by mass.
  • the ink according to the present disclosure may contain at least one organic solvent.
  • organic solvent examples include ketones such as acetone, methyl ethyl ketone and diethyl ketone; alcohols such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol and tert-butanol; chlorine-based solvents such as chloroform and methylene chloride; benzene, Aromatic solvents such as toluene; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethyl lactate, butyl lactate, isopropyl lactate; ether solvents such as diethyl ether, tetrahydrofuran, dioxane; ethylene glycol monomethyl ether, ethylene glycol Glycol ether-based solvents such as dimethyl ether and propylene glycol monomethyl ether; and glycol ether acetate-based solvents such as propylene glycol monomethyl ether acetate can be mentioned.
  • the content of the organic solvent is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total amount of the ink.
  • the ink according to the present disclosure may have a composition that does not contain an organic solvent (that is, the content of the organic solvent is 0% by mass with respect to the total amount of the ink).
  • the ink according to the present disclosure may further contain additives other than siloxane compounds, such as surfactants, ultraviolet absorbers, co-sensitizers, antioxidants, anti-fading agents, and conductive salts.
  • additives other than siloxane compounds, such as surfactants, ultraviolet absorbers, co-sensitizers, antioxidants, anti-fading agents, and conductive salts.
  • publicly known documents such as JP-A-2011-225884 and JP-A-2009-209352 can be appropriately referred to.
  • the viscosity of the ink according to the present disclosure is preferably 10 mPa ⁇ s to 50 mPa ⁇ s, more preferably 10 mPa ⁇ s to 30 mPa ⁇ s, and even more preferably 10 mPa ⁇ s to 25 mPa ⁇ s.
  • Viscosity is a value measured at 25 ° C. using a viscometer. The viscosity is measured, for example, using a VISCOMETER TV-22 type viscometer (manufactured by Toki Sangyo Co., Ltd.).
  • the surface tension of the ink according to the present disclosure is preferably 20 mN / m to 45 mN / m, and more preferably 23 mN / m to 30 mN / m.
  • the surface tension is a value measured at 25 ° C. using a surface tension meter.
  • the surface tension is measured using, for example, DY-700 (manufactured by Kyowa Surface Science Co., Ltd.).
  • the inkjet recording method includes a step of ejecting the ink according to the present disclosure onto a substrate by an inkjet recording method (hereinafter, also referred to as an “ink ejection step”), and the ink is ejected onto the substrate. It includes a step of irradiating the ink with active energy rays (hereinafter, also referred to as “active energy ray irradiation step”).
  • the ink according to the present disclosure is ejected onto the substrate by the inkjet recording method.
  • the base material is not particularly limited as long as it can form an ink image, and examples thereof include paper, cloth, wood, metal, and plastic.
  • the paper examples include general printing paper mainly composed of cellulose such as high-quality paper, coated paper, and art paper, and inkjet recording paper. Further, the paper may be provided with an oil-based varnish or a water-based varnish.
  • the base material may be a permeable base material or a non-permeable base material.
  • the "non-permeable” means that the water contained in the ink is absorbed little or not, and specifically, the water absorption amount is 10.0 g / m 2 or less.
  • the inkjet recording method it is possible to obtain an image having excellent curability, especially when a non-permeable base material is used as the base material.
  • the shape of the non-permeable base material is not particularly limited, and may be a three-dimensional shape such as a bottle, a sheet shape, or a film shape.
  • impermeable substrate examples include metals (eg, aluminum), plastics (eg, polyvinyl chloride, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, etc. (Polyethylene, polystyrene, polypropylene, polycarbonate and polyvinyl acetate) and glass.
  • metals eg, aluminum
  • plastics eg, polyvinyl chloride, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, etc.
  • Polyethylene, polystyrene, polypropylene, polycarbonate and polyvinyl acetate glass.
  • the non-permeable substrate preferably contains a thermoplastic resin such as polyvinyl chloride, polyethylene terephthalate, and polypropylene.
  • the non-permeable substrate may be surface-treated.
  • Examples of the surface treatment include corona treatment, plasma treatment, frame treatment, heat treatment, wear treatment, light irradiation treatment (for example, ultraviolet irradiation treatment) and flame treatment.
  • the corona treatment can be performed using, for example, a corona master (manufactured by Shinko Electric Meter Co., Ltd., PS-10S).
  • the conditions for the corona treatment may be appropriately selected according to the type of the impermeable substrate, the composition of the ink, and the like.
  • the corona treatment can be performed, for example, under the following conditions. -Processing voltage: 10 to 15.6 kV -Processing speed: 30 to 100 mm / s
  • the base material may be a transparent base material or a base material laminated with polyethylene or polypropylene.
  • Transparent substrates include glass, quartz, and plastics (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, acrylic resin, chlorinated polyolefin resin, polyether sulfone resin. , Polyethylene terephthalate (PET), polyethylene naphthalate, nylon, polyethylene, polystyrene, polypropylene, polycycloolefin resin, polyimide resin, polycarbonate resin, polyvinyl acetal, etc.).
  • PET Polyethylene terephthalate
  • the transparent substrate may have one layer or two or more layers.
  • the inkjet recording method is not particularly limited as long as it can record an image, and is a known method, for example, a charge control method for ejecting ink by using electrostatic attraction, and a drop using the vibration pressure of a piezo element.
  • the on-demand method pressure pulse method
  • the acoustic inkjet method that converts an electric signal into an acoustic beam and irradiates the ink to eject the ink using the radiation pressure
  • the acoustic inkjet method that heats the ink to form bubbles and applies the generated pressure. It may be any of the thermal inkjet (bubble jet (registered trademark)) methods to be used.
  • the ink subjected to the action of heat energy causes a rapid volume change, and the ink is ejected from the nozzle by the acting force due to this state change.
  • the inkjet recording method for ejecting can be effectively used.
  • the inkjet head used in the inkjet recording method a short serial head is used, and a multipath method in which recording is performed while scanning the head in the width direction of the base material and a recording element corresponding to the entire area of one side of the base material are used.
  • a single-pass method using an arranged line head can be mentioned.
  • a pattern can be formed on the entire surface of the base material by scanning the base material in a direction intersecting the arrangement direction of the recording elements, and a transport system such as a carriage that scans a short head becomes unnecessary.
  • a transport system such as a carriage that scans a short head becomes unnecessary.
  • the movement of the carriage and the complicated scanning control with the base material are not required, and only the base material moves, so that the recording speed can be increased as compared with the multipath method. Therefore, in the inkjet recording method according to the present disclosure, it is preferable to eject ink by a single pass method.
  • the amount of ink ejected from the inkjet head is preferably 1 pL (picolitre) to 100 pL, more preferably 3 pL to 80 pL, and even more preferably 3 pL to 20 pL.
  • the active energy ray irradiation process In the inkjet recording method of the present disclosure, it is preferable to irradiate the ink ejected on the substrate with active energy rays.
  • the polymerizable monomer is polymerized and cured by irradiation with active energy rays.
  • the active energy ray include ⁇ -ray, ⁇ -ray, X-ray, ultraviolet ray, visible light and electron beam.
  • the active energy ray is preferably ultraviolet light (hereinafter, also referred to as “UV”) or visible light, and more preferably ultraviolet light.
  • the exposure amount of the active energy ray is preferably 20 mJ / cm 2 to 10000 J / cm 2 , and more preferably 100 mJ / cm 2 to 7000 mJ / cm 2 .
  • the irradiation time is preferably 0.01 seconds to 120 seconds, more preferably 0.1 seconds to 90 seconds.
  • the irradiation conditions and the basic irradiation method the irradiation conditions and the irradiation method disclosed in Japanese Patent Application Laid-Open No. 60-132767 can be applied.
  • a method in which light sources are provided on both sides of the head unit including an ink ejection device and the head unit and the light source are scanned by a so-called multipath method, or a method in which a separate light source without driving is used is preferable.
  • Mercury lamps, gas lasers and solid-state lasers are mainly used as light sources for ultraviolet irradiation, and mercury lamps, metal halide lamps and ultraviolet fluorescent lamps are widely known.
  • replacement with a GaN (gallium nitride) -based semiconductor ultraviolet light emitting device is extremely useful industrially and environmentally, and UV-LED (light emitting diode) and UV-LD (laser diode) are compact and have a long life. It has high efficiency and low cost, and is expected as a light source for ultraviolet irradiation.
  • the light source for ultraviolet irradiation is preferably a metal halide lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, or a UV-LED.
  • UV-LED examples include a purple LED (manufactured by Nichia Corporation) having a main emission spectrum having a wavelength between 365 nm and 420 nm.
  • a purple LED manufactured by Nichia Corporation
  • US Pat. No. 6,084,250 discloses LEDs capable of emitting ultraviolet light with wavelengths between 300 nm and 370 nm.
  • the peak wavelength of ultraviolet rays is, for example, preferably 200 nm to 405 nm, more preferably 220 nm to 400 nm, and even more preferably 340 nm to 400 nm.
  • the ink ejection step by irradiating the active energy rays in an atmosphere with an oxygen concentration of 1% by volume or less, it is possible to suppress the inhibition of polymerization by oxygen and improve the curability.
  • the lower limit of the oxygen concentration is not particularly limited.
  • the oxygen concentration can be effectively reduced to zero by creating a vacuum or by substituting the irradiation atmosphere with a gas other than air (eg, nitrogen).
  • the oxygen concentration in the active energy ray irradiation step is preferably 0.01% by volume to 1% by volume, more preferably 0.1% by volume to 1% by volume.
  • Examples of the means for controlling the oxygen concentration in the irradiation atmosphere include a method in which the inkjet recording device is closed to create a nitrogen atmosphere or a carbon dioxide atmosphere, and a method in which an inert gas such as nitrogen is allowed to flow.
  • a method for supplying nitrogen for example, there are a method using a nitrogen cylinder and a method using a device for separating only nitrogen gas from the air by utilizing the difference in permeability of oxygen and nitrogen to the hollow fiber membrane.
  • Examples of the method for supplying carbon dioxide include a method using a carbon dioxide cylinder.
  • the inert gas refers to a general gas such as N 2 , H 2 , CO 2 and a rare gas such as He, Ne, Ar. Above all, the inert gas is preferably N 2 from the viewpoint of safety, availability, and cost.
  • the ink ejected on the base material is irradiated with the first active energy ray to form an ink film (that is, a film formed by the ink applied on the base material).
  • first irradiation step a step of curing
  • second irradiation step a step of irradiating the semi-cured ink film with a second active energy ray to perform main curing
  • the readability after the scraping test and the readability after the adhesion test are improved.
  • polymerizing only a part of the polymerizable monomer in the ink film is referred to as “semi-curing”, and irradiation with active energy rays for semi-curing is also referred to as “pinning exposure”.
  • polymerizing substantially all of the polymerizable monomers in the ink film is referred to as “main curing”, and irradiation with active energy rays for main curing is also referred to as "main exposure”.
  • the first irradiation step at least a part of the polymerizable monomer in the ink film is polymerized by irradiating the ink film with the first active energy ray.
  • the second irradiation step substantially all the polymerizable monomers in the ink film are polymerized by irradiating the ink film with the second active energy ray.
  • the exposure amount of the active energy ray is reduced as compared with the case where only the main exposure is performed.
  • the exposure amount of the first active energy ray is preferably 2 mJ / cm 2 to 5000 mJ / cm 2 , and more preferably 20 mJ / cm 2 to 5000 mJ / cm 2 .
  • the irradiation time is preferably 0.01 seconds to 20 seconds, more preferably 0.1 seconds to 10 seconds.
  • the exposure amount of the second active energy ray is preferably 20 mJ / cm 2 to 10000 J / cm 2 , and more preferably 100 mJ / cm 2 to 7000 mJ / cm 2 .
  • the irradiation time is preferably 0.01 seconds to 120 seconds, more preferably 0.1 seconds to 90 seconds.
  • the reaction rate of the ink film after the pinning exposure is preferably 10% to 80%.
  • the reaction rate of the ink film after the main exposure is preferably more than 80% and 100% or less, more preferably 85% to 100%, and even more preferably 90% to 100%.
  • the reaction rate of the ink film means the polymerization rate of the polymerizable monomer in the ink film obtained by high performance liquid chromatography.
  • the reaction rate of the ink film is calculated using the following method.
  • a sample piece having a size of 20 mm ⁇ 50 mm is cut out from the region where the ink film of the base material exists.
  • the cut sample piece is immersed in 10 mL of THF (tetrahydrofuran) for 24 hours to obtain an eluate in which the ink is eluted.
  • the amount of polymerizable monomer (hereinafter referred to as "amount of monomer after irradiation X1”) is calculated by high performance liquid chromatography.
  • non-irradiated monomer amount X0 the amount of the polymerizable monomer
  • Ink reaction rate (%) ((non-irradiated monomer amount X0-post-irradiated monomer amount X1) / unirradiated monomer amount X0) ⁇ 100
  • the time from the time when the ink lands on the substrate to the time when the first active energy ray is irradiated is within 0.5 seconds.
  • the time from the time when the ink lands on the substrate to the time when the second active energy ray is irradiated is not particularly limited.
  • the time from the time when the ink lands on the substrate until the activation energy ray is irradiated is within 1 second. Is preferable. By the main curing immediately after landing, the ink is suppressed from spreading on the base material, and the readability is improved.
  • the inkjet recording method according to the present disclosure may include other steps other than the ink ejection step and the active energy ray irradiation step.
  • steps include a drying step of drying the ink ejected onto the substrate after the ink ejection process.
  • the drying means and the drying temperature in the drying step can be appropriately adjusted.
  • Speedcure7010L (manufactured by Rambson) and FLORSTAB UV12 (manufactured by Kromachem) were used for the preparation of the ink.
  • Speedcure7010L is a mixture of Speedcure7010 and EOTMPTA, and the mixing ratio is 1: 1 on a mass basis.
  • Speedcure7010 is described in the column of polymerization initiator
  • EOTMPTA is described in the column of polymerizable monomer.
  • FLORSTAB UV12 is a mixture of N-nitroso-N-phenylhydroxylamine aluminum salt and PEA, and the mixing ratio is 1: 9.
  • N-nitroso-N-phenylhydroxylamine aluminum salt was described in the column of polymerization inhibitor, and PEA was described in the column of polymerizable monomer.
  • ⁇ Pigment derivative> ⁇ Pigment derivative 1 having an acidic functional group ... SOLSPERSE 5000S (manufactured by Lubrizol Japan), phthalocyanine copper having a sulfo group ⁇ Pigment derivative 2 having an acidic functional group 2 ... SOLSPERSE 12000S (manufactured by Lubrizol Japan Co., Ltd.), having a sulfo group Phthalocyanine Copper / pigment derivative having a basic functional group ...
  • Product name "EFKA PX 4701” (manufactured by BASF) :, Weight average molecular weight: 22000, SP value: 32.73 MPa 1/2 .
  • -Block polymer 2 having a basic functional group ...
  • Product name "DISPERBYK 191” (manufactured by BYK), weight average molecular weight: 12000, SP value: 33.55 MPa 1/2 .
  • -Block polymer 1 having an acidic functional group ...
  • Product name "DISPERBYK-2001” (manufactured by BYK) :, Weight average molecular weight: 3500, SP value: 22.68 MPa 1/2 .
  • the SP value of the dispersant is the following K.I. W. SUH, J.M. M. It was calculated using the CORBETT formula (Journal of Applied Polymer Science, 12, 2359, 1968).
  • the SP values of acetone, hexane, and deionized water were calculated using HSPiP (version 4.1.07) software.
  • the unit of the obtained SP value is (cal / cm 3 ) 1/2 . Based on the fact that 1 (cal / cm 3 ) 1/2 ⁇ 2.05 MPa 1/2 , the unit was converted from (cal / cm 3 ) 1/2 to MPa 1/2 .
  • -MPDDA Product name "SR341" (manufactured by Sartomer), 3-methyl-1,5-pentanediol diacrylate, SP value: 17.60 MPa 1/2 , Tg: 105 ° C.
  • -DPGDA Product name "DPGDA” (manufactured by Dycel Ornex), dipropylene glycol diacrylate, SP value: 17.73 MPa 1/2 , Tg: 104 ° C.
  • IBOA Product name "SR506NS” (manufactured by Sartomer), isobornyl acrylate, SP value: 17.10 MPa 1/2 , Tg: 97 ° C.
  • -TCDDMDA Product name "SR833S” (manufactured by Sartomer), tricyclodecanedimethanol dimeacrylate, SP value: 17.85 MPa 1/2 , Tg: 186 ° C.
  • -TMPTA Product name "TMPTA” (manufactured by Dycel Ornex), trimethylolpropane triacrylate, SP value: 17.43MPa 1/2 , Tg: 27 ° C.
  • ACMO Product name "ACMO” (manufactured by RAHN), acryloylmorpholine, SP value: 22.39 MPa 1/2 , Tg: 145 ° C.
  • EOTMPTA Trimethylolpropane EO-added triacrylate, SP value: 17.72 MPa 1/2 , 50% by mass contained in Speedcure7010L (manufactured by Rambson), Tg: 90 ° C. -PEA ... Phenoxyethyl acrylate, SP value: 19.44 MPa 1/2 , 90% by mass contained in FLORSTAB UV12 (manufactured by Kromachem), Tg: 5 ° C.
  • Tg glass transition temperature
  • EXSTAR6220 differential scanning calorimeter
  • the SP value of the polymerizable monomer was calculated based on the following formulas A and B1 to B3.
  • the dispersion term, polarity term, and hydrogen bond term of each polymerizable monomer contained in the ink are as shown in Table 1.
  • the variance term ⁇ d, the polarity term ⁇ p, and the hydrogen bond term ⁇ h are values calculated using HSPiP (version 4.1.07) software.
  • SP value ( ⁇ ) [MPa 1/2 ] ( ⁇ d 2 + ⁇ p 2 + ⁇ h 2 ) 1/2 ...
  • A) ⁇ d ⁇ d m W m / ⁇ W m ...
  • ⁇ p ⁇ p m W m / ⁇ W m ...
  • ⁇ dm the dispersion term of the polymerizable monomer of the m item (m represents an integer of 1 or more) in the polymerizable monomer.
  • ⁇ pm represents the polarity term of the polymerizable monomer of the m item (m represents an integer of 1 or more) in the polymerizable monomer.
  • ⁇ h m represents the hydrogen bond term of the polymerizable monomer of the m item (m represents an integer of 1 or more) in the polymerizable monomer.
  • W m represents the content ratio (mass%) of the above-mentioned m-type polymerizable monomer to the total amount of the polymerizable monomer.
  • the calculated SP values of the polymerizable monomer are shown in Tables 2 to 6.
  • ⁇ siloxane compound> -BYK-307 (manufactured by BIC Chemie): polysiloxane without a polymerizable group-TEGORAD 2100 (manufactured by Degussa): polysiloxane having a polymerizable group
  • Example 7 Each component was mixed so as to have the following composition, and pre-dispersion was performed for 30 minutes using a stirrer. Then, using a batch type bead mill (product name "Easy Nano RMB", manufactured by AIMEX), dispersion treatment was performed at 1000 rpm (rotation speed / min) for 4.5 hours using zirconia beads having a diameter of 0.5 mm ⁇ . .. Filtration was performed using a 67 ⁇ m filter cloth and a 5 ⁇ m filter to obtain a dispersion liquid A1.
  • Examples 1 to 6, 8 to 25, Comparative Examples 1 to 6 A dispersion was prepared by the same method as in Example 7 except that the content of each component contained in the ink was changed to the content (% by mass) shown in Tables 2 to 5. Ink was prepared.
  • the readability, the readability after aging, the readability after the transfer test, the readability after the close contact test, and the readability after the scraping test were evaluated.
  • the evaluation results are shown in Tables 2 to 5.
  • the “SP value difference” means the difference between the calculated SP value of the polymerizable monomer and the SP value of the dispersant.
  • the "ratio of monomers having a Tg of 30 ° C. or higher” means the proportion of polymerizable monomers having a glass transition temperature of 30 ° C. or higher in all the polymerizable monomers.
  • Comparative Example 6 the curability was insufficient, and the readability after the transfer test, the readability after the close contact test, and the readability after the scraping test could not be evaluated. Therefore, “-” in Table 5 It was described.
  • a photographic base material (product name "painting photo finish gloss premium", manufactured by FUJIFILM Corporation) was superposed on the obtained image recording material. It was pressed from above the photographic substrate with a load of 5 N for 3 seconds. Twenty locations were randomly selected from the image recording material after the photographic substrate was peeled off, and it was determined whether or not the image could be read using an IR detector. The readability after the transcription test was evaluated based on the number of read sites. The evaluation criteria are as follows. A: It was read at 15 to 20 places. B: It was read at 10 to 14 places. C: It was read at 5 to 9 places. D: I could't read at one place, or I could read at 1 to 4 places.
  • Examples 1 to 25 include a near-infrared absorbing dye represented by the formula 1, a polymerizable monomer, a polymerization initiator, and a dispersant, and contain a polymerizable monomer.
  • the amount is 50% by mass or more with respect to the total amount of the ink for inkjet recording, and the difference between the SP value of the polymerizable monomer and the SP value of the dispersant is 3.8 MPa 1/2 to 16.0 MPa 1/2 . Therefore, it was found that an image recording material having excellent readability and readability after a lapse of time can be obtained.
  • Comparative Example 1 it was found that the readability and the readability after a lapse of time were inferior because the near-infrared absorption dye represented by the formula 1 was not contained.
  • Example 3 the molecular weight of the dispersant was 50,000 or less, and the readability was excellent as compared with Example 1.
  • Example 5 the dispersant was a block polymer, and it was found that the dispersant was excellent in readability after a lapse of time as compared with Example 3.
  • Example 7 contained a pigment derivative and was superior in readability after a lapse of time as compared with Example 5.
  • Example 9 contained a siloxane compound and was superior in readability after the scraping test as compared with Example 7.
  • Examples 11 to 13 contained a siloxane compound having a polymerizable group, and were excellent in readability after the transfer test and readability after the adhesion test as compared with Example 9.
  • Example 13 the content of the siloxane compound having a polymerizable group is 0.5% by mass to 3% by mass with respect to the total amount of the ink, and each evaluation is compared with Examples 11 and 12. It turned out to be excellent overall.
  • Example 15 contained an acylphosphine oxide compound and a thioxanthone compound, and was found to be superior in readability after the transfer test as compared with Example 13.
  • Example 17 the proportion of the polymerizable monomer having a glass transition temperature of 30 ° C. or higher in the polymerizable monomer is 90% by mass or more, and the readability after the scraping test is excellent as compared with Example 15. Do you get it.
  • Example 26 The same ink as in Example 24 was introduced into the sixth throttle of a single-pass inkjet printer (“Jet Press 540WV” manufactured by Fujifilm Corporation). A PET (polyethylene terephthalate) film was prepared as a base material. The ink was ejected from the inkjet head of the inkjet printer, and an image having a halftone dot ratio of 3% was applied onto the substrate by a single pass method.
  • the ink application conditions were 600 dpi ⁇ 600 dpi, a single pass method, and a substrate transfer speed of 50 m / min.
  • the ink applied on the substrate was irradiated with the active energy ray A as an exposure for the main curing in 0.1 seconds from the time when the ink landed.
  • the active energy ray A is ultraviolet light having a peak wavelength of 385 nm.
  • the exposure amount of the active energy ray A was 6600 mJ / cm 2 .
  • the obtained image recording material was evaluated for readability, readability after aging, readability after transfer test, readability after close contact test, and readability after scraping test by using the above evaluation method. went. The evaluation results were all A.
  • Example 27 Ink was applied onto the substrate in the same manner as in Example 26. Next, the ink applied on the substrate was irradiated with the first active energy ray as an exposure for semi-curing and the second active energy ray as an exposure for main curing in this order. The time from the time when the ink lands to the irradiation of the first active energy ray is 0.1 seconds, and the time from the time when the ink lands to the time when the second active energy ray is irradiated is 2.0 seconds. there were. Both the first active energy ray and the second active energy ray are ultraviolet rays having a peak wavelength of 385 nm.
  • the exposure amount of the first active energy ray was 350 mJ / cm 2
  • the exposure amount of the second active energy ray was 6600 mJ / cm 2 .
  • the obtained image recording material was evaluated for readability, readability after aging, readability after transfer test, readability after close contact test, and readability after scraping test by using the above evaluation method. went. The evaluation results were all A.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne une encre d'impression à jet d'encre et un procédé d'impression à jet d'encre, un pigment absorbant le proche infrarouge, un monomère polymérisable, un initiateur de polymérisation et un dispersant exprimés par la formule (1) suivante étant compris, la teneur du monomère polymérisable étant de 50 % en masse ou plus par rapport à la quantité totale de l'encre d'impression à jet d'encre, et une différence entre une valeur SP du monomère polymérisable et une valeur SP du dispersant étant de 3,8 MPa1/2 à 16,0 MPa1/2. Dans la formule (1), des descriptions d'un cycle (A), d'un cycle (B), de XA, XB, GA, GB, kA et kB sont omises.
PCT/JP2021/025956 2020-09-11 2021-07-09 Encre d'impression à jet d'encre et procédé d'impression à jet d'encre WO2022054387A1 (fr)

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CN202180061669.XA CN116096576A (zh) 2020-09-11 2021-07-09 喷墨记录用油墨及喷墨记录方法
EP21866347.4A EP4212341A4 (fr) 2020-09-11 2021-07-09 Encre d'impression à jet d'encre et procédé d'impression à jet d'encre
JP2022547414A JP7451730B2 (ja) 2020-09-11 2021-07-09 インクジェット記録用インク及びインクジェット記録方法
US18/167,880 US20230203330A1 (en) 2020-09-11 2023-02-12 Ink jet recording ink and ink jet recording method

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WO2023053925A1 (fr) * 2021-09-30 2023-04-06 富士フイルム株式会社 Encre d'enregistrement par jet d'encre et procédé d'enregistrement par jet d'encre
WO2023105206A1 (fr) * 2021-12-07 2023-06-15 Fujifilm Speciality Ink Systems Limited Encre d'impression

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Publication number Priority date Publication date Assignee Title
WO2023053925A1 (fr) * 2021-09-30 2023-04-06 富士フイルム株式会社 Encre d'enregistrement par jet d'encre et procédé d'enregistrement par jet d'encre
WO2023105206A1 (fr) * 2021-12-07 2023-06-15 Fujifilm Speciality Ink Systems Limited Encre d'impression

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US20230203330A1 (en) 2023-06-29
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JPWO2022054387A1 (fr) 2022-03-17
JP7451730B2 (ja) 2024-03-18

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